Oct. 5, 1952
NOTES
Calcd. for ClbH24OloSa: C, 55.55; H , 4.48; S, 10.37. Found: C, 55.4; H, 4.60; N, 10.3. Quinine salt of PCA: m.p. 207-209'. A n d . Calcd. for C ~ ~ H ~ I O S C,N66.20; ~: H, 6.89; N, 9.27. Fourid: C, 66.3; H, 6.90; 3,9.3. Quinine salt of Me K-PCA: m.p. 159-160'. '4naZ. Calcd. for C51H62010Ss: C, 66.65; H , 6.80; S, 9.15. Found: C , 66.5; H , 6.76; S , 9.1.
4967
metal is deposited in the apparatus, probably as the result of reduction or thermal decomposition of the penta- or tribromide. This reaction is also slowed by the formation of a green powder (tantalum tribromide) on the surface of the unreacted metal. Tantalum Pentachloride and Tantalum.Schafer and Pietruck3 have shown that tantalum Acknowledgments.-The authors are grateful for pentachloride is not reduced by the metal a t 350the cooperation of K. J. Palmer on the X-ray stud- 400" in an .evacuated tube, an observation which ies, F. T . Jones on the optical measurements, and was also made in the course of the present work. Geraldine Secor and Mary Kilpatrick on the com- In the range 475-500", however, a small amount of position analyses. a green chloride is formed. If the unreacted penWESTERN REGIONAL RESEARCH LAB. tachloride is sublimed away in vacuo and the green 6, CALIF. ALBANY material is dissolved in water, one obtains a green solution in which the chlorine to tantalum ratio is 3.35 and the average oxidation state of the tantalum Reaction of Tantalum with Hydrogen Chloride, Hydrogen Bromide and Tantalum Pentachloride ; is 3.29. This latter value was obtained electroAction of Hydrogen on Tantalum Pentachloride metrically by use of platinum and saturated calomel electrodes and a potassium nitrate-agar salt BY RALPHC. YOUNGAND CARLH. BRUBAKER, JR. bridge. Ceric sulfate was the oxidant. When the RECEIVED MAY19, 1952 inflection in the plot of e.m.f. vs. volume of titrant Hydrogen Chloride and Tantalum.-When hy- was noted, a brown flocculent precipitate (cf. drogen chloride gas is passed over tantalum metal TaOz,xHzO) was present in the solution. It was a t 410" and above, white tantalum pentachloride is assumed that the tantalum was then in oxidation formed and can be collected upon a cold-finger state (IV). These analyses would indicate the condenser. IVhen the temperature is elevated to presence of some tantalum in a lower oxidation 600-750", a thin film of metal, containing dissolved state (probably 111) and possibly a compound hydrogen, is formed on the heated tube walls. This such as TasCllo. Hydrogen and Tantalum Pentachloride.-Alinetal is probably formed by the reduction or thermal decomposition of the pentachloride or some though niobium pentachloride is readily reduced ,~ and lower chloride, which may begin to form and im- with hydrogen to form the t r i ~ h l o r i d eSchafer mediately disproportionate (cf.Ruff and Thomas,'S2 Pietruck3 have shown that tantalum pentachloride on TaCL) a t the higher temperature. ilfter the re- is not affected a t temperatures up to 400". Studaction has proceeded (600-750") for a few hours, i t ies in the course of the present work resulted in the is slowed markedly and an olive colored powder same conclusions. However, if the reaction is carforms on the surface of the unreacted metal. ried out a t 500", some reduction of the pentachloChemical properties and analyses indicate that the ride does occur and a film of the product, tantalum olive powder is tantalum dichloride as described by metal, containing dissolved hydrogen, is deposited on the heated walls of the reduction tube. KO Ruff and Thomas.1,3 The tantalum dichloride powder (mixed with lower chlorides could be detected. This is in conmetal) was treated with 1 M potassium hydroxide trast to the reduction of the pentabromide by hyand the residual tantalum was filtered away. drogen. The formation of tantalum tribromide \Then the solution was heated, hydrogen bubbled has been reported by Van Haagen5 and by Young off and a dark flocculent precipitate (presumably and Hastings.6 (3) H. Schafer and C. Pietruck, Z . anovg. allgem. C h e m . , 266, 151 TaOz.xH20) formed. The tantalum was oxidized (1951). with nitric acid, the pentoxide thus formed was (4) C. H. Brubaker, J r . , and R. C. Young, THISJ O U R N A L , 73, 4179 filtered off and chlorine was determined as silver (1931). ( 3 ) W. K . V a n Haagen, Thesis, University uf Pennsylvania, I'JO'J chloride in the filtrate (Anal. Cl/Ta = 1.97). Friend, "Textbook of Inorganic Chemistry," Vol. V I , p. 1951 The metallic tantalum films were fused with (from (6) R. C . Young and T. H. Hastings, J r . , THISJ O U R N A L , 64, 1740 sodium carbonate and, during the fusion, consider- (1942). able adsorbed hydrogen gas escaped and burned. DEPARTMENT OF CHEMISTRY The cooled melts were dissolved in water and the MASSACHUSETTS ISSTITUTE OF TECHNOLOGY solutions were acidified with nitric acid. The CAMBRIDGE 39, MASSACHUSETTS weights of pentoxide thus formed indicated the metallic films were tantalum (99.97, Ta or higher.) 0 3,0 4,N-Triacetyl-(- )-epinephrine Hydrogen Bromide and Tantalum.-If 'hydrogen bromide is passed over metallic tantalum a t 375", BY LLEWELLYN H. WELSH tantalum pentabromide is formed and if the temRECEIVED MARCH21, 1952 perature is maintained a t 550" or above, some triThe action of excess acetic anhydride on an bromide begins to form, apparently mixed with a still lower bromide or perhaps the metal. Anal. aqueous solution of ephedrine in the presence of Calcd. for TaBrs: Ta, 48.0; Rr, .57.0. Found: bicarbonate yields the N-monoacetyl derivative. When essentially the same procedure is applied to Ta, 44.7; Br, 53.5. At higher temperatures (up to 800") tantalum (,-)-epinephrine (Ia), there is obtained a quantitative yield of a crystalline, levorotatory triacetyl (1) 0 Ruff and F. Thomas, B P K ,55, 1466 (1922). (2) 0 . Ruff a n d F. Thomas, Z
aizo~'~ d i. g e m .
C h e m . , 148, 1 ( 1 9 2 5 ) .
(1) L. H . Welsh, .7. A m . P h a r m . A s s o c . , 36, 373 (1947).
derivative, melting, when pure, at 94-95". Its neutral nature and its failure to give a color reaction R
~ H OH C CH
O RO
s( K c H
Ia, R = H I b , R = CHaCO
etnployed to advantage in the isolation, identification and estimation of epinephrine. Resistance of the alcoholic hydroxyl group of ephedrine and epinephrine toward acetylation under the experimental conditions appears noteworthy. In the presence of as much as 15 to 30 molecular proportions of anhydride, this functional group remains virtually, if not literally, intact while the amino and phenolic functions are quantitatively acetylated.
in the presence of ferric chloride demonstrate that acylation of the amino nitrogen and phenolic hydroxyl groups has occurred, and permit the identification of the product as O3,O4,N-triacety1Experimental (-)-epinephrine (Ib).2 Its ultraviolet3 and infraFinely powdered ( -)-epinephrine5 (2.00 g., 0.0109 mole) red4 absorption spectra are shown in Figs. 1 and 2 , was added to a mixture of 60 g. of sodium bicarbonate and respectively. 200 cc. of water in a 1-1. erlenmeyer flask. While the system was vigorously stirred by a motor-driven wire stirrer, 30
0.8
0.6
rJ 0
k 0.4 I?
c
Y
0.2
0 280 260 240 Wave length in mp. Fig. 1.-Ultraviolet absorption spectrum of triacetylepinephrine taken in 957, ethanolic solution (400 mg./ 1.) with a model 11 Carey spectrophotometer (I-cni cell): €271 518, €264 573.
cc. (0.32 mole) of reagent grade acetic anhydride was added cautiously in 4 equal portions. Violent foaming was controlled by the addition of a few drops of ether. When the evolution of carbon dioxide had ceased after the last addition of anhydride, the mixture was allowed to stand about five minutes then extracted with sis 100-cc. portions of chloroform. The filtered extracts were concentrated on the steatnbath to an oil which w-as induced to crystallize by adding ether and triturating. The yield of almost white product was quantitative ( 3 . 3 5 g.j; 1i1.p.91-93' (cor.). It was recrystallized with 90% recovery by dissolving it in acetone (1.3 cc./n.) and addim 7 volumes of ether. Thrice-recrystallizgd'material ha; m.p. 94-95' (cor.), [CY]% -94.7" (U.S.P. CHCla, c 1.01). Anal. Calcd. for ClsHl,SO~:C, 58.24; H , 6.19; N , 4.53. Found: C, 58.17, 58 28; H, 6.10, 6.08; S (Kjeldahl),6 4.45, 4.53. From acetone-ether, the substance crystallizes as platy or tabular prisms: rpfractive indices, 01 = 1.516, B = 1.527, -( = 1.572 (all =!= 0.002), optic sign, biaxial positive; optic angle, 2 V = 52' (from microscopic observation of interference figure aiid calculated from refractive indices); extinct i m i , both par~llel atid inclined; system, probably monoClllllC
(.i) Prepared f r o m lVinthrop-Stearns synthetic (-)-epinephrine with ammoilia: [ c z ] " ' ~ -51.1' (c 2 in 0.3 S bitdrtrate by ~~r?vipilatiun hydrochloric r l c i < i ) . l f i ) Uztzrrninatioiir by Charles Graichrn, L)ivi,ion of CIVISIOS O F PHARMACEUTICAL CHEMISTRY FOOD & DRUGADMINISTRATION VEDERAL SECURITY AGENCY \VASAINGTON 23, 11. C.
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